Dialkenyl-tricyclic-nonaromatic/olefin polymers

ABSTRACT

A process is provided to produce a dialkenyl-tricyclic-nonaromatic/olefin polymer. The process comprises contacting at least one dialkenyl-tricyclic-nonaromatic compound, at least one olefin, at least one titanium complex, and at least one aluminoxane in a polymerization zone under polymerization conditions to form the dialkenyl-tricyclic-nonaromatic/olefin polymer.

FIELD OF THE INVENTION

[0001] This invention is related to the field of polymers comprising apolymerized dialkenyl-tricyclic-nonaromatic compound and a polymerizedolefin.

BACKGROUND OF THE INVENTION

[0002] Polymer compounds represent a very important and highly versatilematerial of construction. They have become truly indispensable and areessential for clothing, shelter, transportation, and many conveniencesof modem living. Therefore, there is a strong market for polymersthroughout the world resulting in billions of dollars of sales per year.Most plastics can be easily fabricated into various products by suchprocesses, for example, as blow molding, injection molding, andthermoforming. There is a significant amount of research conducted tofind new polymers to supply the demand for such lightweight andversatile materials.

[0003] Processes that currently form polymers comprising adialkenyl-tricyclic-nonaromatic compound as shown in Formula I:

[0004] where R can be selected from the group consisting of hydrogen andalkyl groups having 1 to about 4 carbon atoms, and an olefin can producea crosslinked polymer. Polymers that form crosslinking with each otheror with other compounds can be insoluble and stable to heat. Thesepolymers generally cannot be dissolved to allow admixture with othercompounds or to flow or melt to form articles. It is desirable toproduce a dialkenyl-tricyclic-nonaromatic/olefin polymer that is notcrosslinked since it could be utilized for various applications.

[0005] Applicants provide such a process for producing adialkenyl-tricyclic-nonaromatic/olefin polymer that is not crosslinked.

SUMMARY OF THE INVENTION

[0006] An object of this invention is to provide a process that producesa dialkenyl-tricyclic-nonaromatic/olefin polymer that is notcrosslinked.

[0007] Another object of this invention is to provide thedialkenyl-tricyclic-nonaromatic/olefin polymer.

[0008] In accordance with one embodiment of this invention, a process toproduce the dialkenyl-tricyclic-nonaromatic/olefin polymer is provided.The process comprises (or optionally, “consists essentially of”, or“consists of”) contacting:

[0009] 1) at least one dialkenyl-tricyclic-nonaromatic compound;

[0010] 2) at least one olefin;

[0011] 3) at least one titanium complex; and

[0012] 4) at least one aluminoxane;

[0013] in a polymerization zone under polymerization conditions to formthe dialkenyl-tricyclic-nonaromatic/olefin polymer.

[0014] In accordance with another embodiment of this invention, thedialkenyl-tricyclic-nonaromatic/olefin polymer is provided.

[0015] In accordance with yet another embodiment of this invention, anarticle is produced comprising thedialkenyl-tricyclic-nonaromatic/olefin polymer.

[0016] This object, and other objects, will become more apparent tothose with ordinary skill in the art after reading this disclosure.

DETAILED DESCRIPTION OF THE INVENTION

[0017] A process to produce a dialkenyl-tricyclic-nonaromatic/olefinpolymer is provided. The process comprises contacting:

[0018] 1) at least one dialkenyl-tricyclic-nonaromatic compound;

[0019] 2) at least one olefin;

[0020] 3) at least one titanium complex; and

[0021] 4) at least one aluminoxane in a polymerization zone underpolymerization conditions to form thedialkenyl-tricyclic-nonaromatic/olefin polymer.

[0022] The dialkenyl-tricyclic-nonaromatic compound has the formula:

[0023] wherein R can be selected from the group consisting of hydrogenand alkyl groups having from 1 to about 4 carbon atoms. Preferably, thedialkenyl-tricyclic-nonaromatic compound is dicyclopentadiene (DCPD).

[0024] The olefin that can be used in this invention contains from 2 toabout 20 carbon atoms. However, it is more preferred when the olefincontains 2 to about 10 carbon atoms. It is most preferred when theolefin has 2 to 6 carbon atoms. Olefins can be selected from the groupconsisting of ethylene, propylene, butylene, pentene, and hexene.Ethylene is currently most preferred.

[0025] The dialkenyl-tricyclic-nonaromatic compound and the olefin arepolymerized using at least one titanium complex. The titanium complexhas the following general formula:

(X¹)(X²)(X³)(X⁴)M¹

[0026] wherein M¹ is titanium;

[0027] wherein (X¹) is independently selected from the group consistingof cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls;

[0028] wherein substituents on the substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls of (X¹) are selectedfrom the group consisting of aliphatic groups, cyclic groups,combinations of aliphatic and cyclic groups, silyl groups, alkyl halidegroups, halides, organometallic groups, phosphorus groups, nitrogengroups, oxygen groups such as, alkoxides and aryloxides, silicon,phosphorus, boron, germanium, and hydrogen; and

[0029] wherein (X²), (X³), and (X⁴) are independently selected from thegroup consisting of halides, aliphatic groups, substituted aliphaticgroups, cyclic groups, substituted cyclic groups, combinations ofaliphatic groups and cyclic groups, combinations of substitutedaliphatic groups and cyclic groups, combinations of aliphatic groups andsubstituted cyclic groups, combinations of substituted aliphatic groupsand substituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkoxide groups,substituted alkoxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups.

[0030] Examples of suitable titanium complexes include, but are notlimited to:

[0031] n⁵cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titanium(IV)dichloride;

[0032] bis(n⁵-cyclopentadienyldichlorotitanium)oxide;

[0033] n⁵-cyclopentadienyl(3,5-di-tert-butylphenoxy)titanium(IV)dichloride; and

[0034] n⁵-cyclopentadienyl(N,N-bis(trimethylsilyl)amido)titanium(IV)dichloride Preferably, the titanium complex is

[0035] n⁵-cyclopentadienyl titanium(IV) trichloride.

[0036] Aluminoxanes are cyclic or linear polymeric aluminum compounds.Cyclic aluminoxanes are represented by the formula (R—Al—O)_(n), andlinear aluminoxanes are represented by the formula R(R—Al—O—)_(n)AlR. Ris an alkyl group having from 1 to about 5 carbon atoms per radical,such as, for example, methyl, ethyl, propyl, butyl, and pentyl, and n isan integer from 1 to about 20. Most preferably, R is methyl, and n isabout 4.

[0037] The polymerization is conducted in a polymerization zone. Thepolymerization can be conducted in a solution polymerization process ora slurry polymerization process. A solution polymerization process ispreferred. In the solution polymerization process, a hydrocarbon solventcapable of dissolving the dialkenyl-tricyclic-nonaromatic compound,olefin, titanium complex, and the dialkenyl-tricyclic-nonaromatic/olefinpolymer is utilized. The solvent can be selected from the groupconsisting of hexane, cyclohexane, toluene, benzene, xylene,t-butylbenzene, and mixtures thereof. Preferably, the solvent istoluene.

[0038] In a solution polymerization process, the temperature is in arange of about 0° C. to about 300° C. However, it is more preferred whenthe temperature is in a range of about 20° C. to about 200° C., and itis most preferred when the temperature is in a range of 50° C. to 120°C.

[0039] In a solution polymerization process, the pressure is in a rangeof about 100 kPa to about 10000 kPa. However, it is more preferred whenthe pressure is in the range of about 500 kPa to about 6000 kPa, and itis most preferred when the pressure is in the range of 500 kPa to 5000kPa.

[0040] If a slurry polymerization process is utilized, it is preferredto use a loop slurry reactor. These reactors are well known in thepolyethylene polymerization art.

[0041] The dialkenyl-tricyclic-nonaromatic/olefin polymer produced bythis process comprises about 0.1 to about 90 weight percent polymerizeddialkenyl-tricyclic-nonaromatic compound based on the weight of thedialkenyl-tricyclic-nonaromatic/olefin polymer. However, it is morepreferred when the dialkenyl-tricyclic-nonaromatic/olefin polymerproduced by this process comprises about 20 to about 90 weight percentpolymerized dialkenyl-tricyclic-nonaromatic compound based on the weightof the dialkenyl-tricyclic-nonaromatic/olefin polymer, and it is mostpreferred when the dialkenyl-tricyclic-nonaromatic/olefin polymerproduced by this process comprises 40 to 80 weight percent polymerizeddialkenyl-tricyclic-nonaromatic based on the weight of thedialkenyl-tricyclic-nonaromatic/olefin polymer.

[0042] In a more specific embodient of this invention, a process isprovided to produce an ethylene/DCPD polymer. The process comprisescontacting n⁵-cyclopentadienyl titanium(IV) trichloride, ethylene,dicyclopentadiene, and methylaluminoxane in a solution polymerizationprocess to produce the ethylene/DCPD polymer.

[0043] The dialkenyl-tricyclic-nonaromatic/olefin polymer produced isnot crosslinked. There is no ring opening as a result of thepolymerization reaction. The non-crosslinking of thedialkenyl-tricyclic-nonaromatic/olefin polymer is indicated by itsability to dissolve in a solvent at 70° C., such as, for example,trichlorobenzene. Crosslinked polymers typically can be insoluble evenat higher temperature. Further evidence of no crosslinking is thenuclear magnetic resonance (NMR) spectrum of thedialkenyl-tricyclic-nonaromatic/olefin polymer shows peaks in theolefinic region of the spectrum which confirms the fact that thenon-reacting double bond is still intact. In addition, the spectrumshows that the 5,6-double bond (i.e norbornene ring alkenyl constituent)is the one that is polymerizing.

[0044] Divinyl-dicyclo-nonaromatic/olefin polymers can be utilized toproduce package film, medical equipment, such as syringes or vials, andoptical equipment, such as data storage media, industrial lenses,ophthalmic lenses, projection lenses, automotive lenses, and lampreflectors.

EXAMPLES

[0045] Polymerization Process

[0046] The following polymerization procedure was utilized in all of theexamples. First, varying amounts of 86 to 98 wt % DCPD in toluene werecharged to a dry, 1 gallon reactor, which was then heated to 70° C. Thespecific amounts of DCPD used are specified in Table 1. In Examples1-10, 200 milliliters of polymerization grade toluene were charged tothe reactor; however in Examples 11-12, the 200 milliliters of toluenewere not added. Then, the reactor was pressured to 150 psig withethylene and then depressured. This pressure/depressure cycle wascompleted three times. Ethylene was then charged to maintain a pressureof 100 psig in the reactor. Then, the ethylene pressure was increased to300 psig and maintained for 15 minutes while the reactor was stirred.The ethylene flow was then stopped, and the reactor was vented to 50 or100 psig. 10-30 milliliters of 10 wt % methylaluminoxane (MAO) intoluene and 0.01 to 0.04 grams of a titanium complex were then chargedto the reactor. The ethylene flow to the reactor was re-established atbetween 50 and 300 psig and maintained for between 60 to 90 minutes toproduce an ethylene/dicyclopentadiene polymer mixture comprisingethylene/dicyclopentadiene polymer, toluene, and unreacted ethylene andDCPD. The ethylene flow was then stopped by adding 5 milliliters ofmethanol, and the reactor was allowed to cool. Theethylene/dicyclopentadiene polymer mixture was then washed and dried ina vacuum oven at 50° C. In some examples, 5 milliliters of anantioxidant solution were also added to the ethylene/dicyclopentadienepolymer mixture prior to drying. The antioxidant solution contained 10weight percent tris(p-nonylphenyl)phosphite (TNPP) and 40 weight percenttetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate incyclohexane. The TNPP was obtained from GE Specialty Chemicals inParkersburg, W. Va. Thetetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate wasobtained as Irganox® 1076 from Ciba-Geigy Corporation in Hawthorne, N.Y.

Example 1

[0047] In this example,n⁵-cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titanium(IV)dichloride was used to polymerize ethylene and 50 grams of 98% by weightDCPD in toluene by the polymerization procedure discussed previously. 10milliliters of 10 wt % MAO in toluene were added during thispolymerization. 212 grams of an ethylene/dicyclopentadiene polymermixture were obtained. The ethylene/dicyclopentadiene mixture then wasdried in a vacuum oven to yield an ethylene/dicyclopentadiene polymerwith a dry weight of 0.8 grams. The activity of then⁵-cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titanium(IV)dichloride was 80 grams of ethylene/dicyclopentadiene polymer per gramof n⁵-cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titanium(IV)dichloride per hour.

Example 2

[0048] In this example,n⁵-cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titanium(IV)dichloride was used again to polymerize ethylene and DCPD in toluene asin Example 1 except during this experiment 110 grams of 91.5% by weightDCPD in toluene were added to the reactor. 26.3 grams of anethylene/dicyclopentadiene polymer mixture were obtained. Theethylene/dicyclopentadiene polymer mixture was washed with 1% by weightHCl, then washed with water, and finally the ethylene/dicyclopentadienepolymer was washed with acetone. The ethylene/dicyclopentadiene polymerwas dried in a vacuum oven to a dry weight of 2.9 grams yielding anactivity of 290 grams of ethylene/dicyclopentadiene polymer per gram ofn⁵-cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titanium(IV)dichloride per hour.

Example 3

[0049] In this example,n⁵-cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titanium(IV)dichloride was used to polymerize ethylene and DCPD as in Example 2except during this polymerization 30 milliliters of 10 wt % MAO intoluene were added to the reactor. In addition, the antioxidant solutiondiscussed previously was added to the ethylene/dicyclopentadiene polymermixture. Soft white ethylene/dicyclopentadiene polymer was produced. Theethylene/dicyclopentadiene polymer mixture was washed with 1% by weightHCl and then washed with acetone. The polymer was dried in a vacuum ovento a dry weight of 35.6 grams yielding an activity of 3560 grams ofethylene/dicyclopentadiene polymer per gram ofn⁵-cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titanium(IV)dichloride per hour.

Example 4

[0050] Bis(n⁵-cyclopentadienyldichlorotitanium) oxide was used for thispolymerization. 30 milliliters of 10 wt % MAO in toluene and 110 gramsof 91.5 wt % DCPD in toluene were added to the reactor. Fluff typepolymer was produced. The ethylene/dicyclopentadiene polymer mixture waswashed with acetone and dried in a vacuum oven to produce a dry weightof 51.4 grams. This catalyst had an activity of 5140 grams ofethylene/dicyclopentadiene polymer per gram ofbis(n⁵-cyclopentadienyldichlorotitanium) oxide per hour.

Example 5 & 6

[0051] In Example 5,n⁵-cyclopentadienyl(3,5-di-tert-butylphenoxy)titanium(IV) dichloride wasused for this polymerization. 30 milliliters of 10 wt % MAO in tolueneand 118 grams of 85 wt % DCPD in toluene were added to the reactor.Fluff type polymer was produced. The ethylene/dicyclopentadiene polymermixture was washed with methanol and contacted with 5 milliliters ofantioxidant solution. The ethylene/dicyclopentadiene polymer mixture wasthen dried in a vacuum oven to produce a dry weight of 13.9 grams. Thiscatalyst had an activity of 1390 grams of ethylene/dicyclopentadienepolymer per gram ofn⁵-cyclopentadienyl(3,5-di-tert-butylphenoxy)titanium(IV) dichloride perhour.

[0052] The experiment in Example 5 was repeated in Example 6 except theethylene/dicyclopentadiene polymer mixture was washed with toluene andthen acetone. It was then dried in a vacuum oven to produce 46.7 gramsof dry polymer which yielded an activity of 4650 grams ofethylene/dicyclopentadiene polymer per gram ofn⁵-cyclopentadienyl(3,5-di-tert-butylphenoxy)titanium(IV) dichloride perhour.

Example 7 & 8

[0053] Bis(n⁵-cyclopentadienyldichlorotitanium) oxide was used for thispolymerization. 30 milliliters of 10 wt % MAO in toluene and 118 gramsof 85 wt % DCPD in toluene were added to the reactor. Theethylene/dicyclopentadiene polymer mixture was dried in a vacuum oven toproduce a dry weight of 41.4 grams. This catalyst had an activity of4140 grams of ethylene/dicyclopentadiene polymer per gram ofbis(n⁵-cyclopentadienyldichlorotitanium) oxide per hour.

[0054] Example 7 was repeated. The ethylene/dicyclopentadiene polymermixture produced was washed with acetone, then toluene, then finallywith methanol. The ethylene/dicyclopentadiene polymer mixture was thendried in a vacuum oven. This polymerization produced 24.9 grams ofpolymer yielding an activity of 2490 grams of ethylene/dicyclopentadienepolymer per gram of bis(n⁵-cyclopentadienyldichlorotitanium) oxide perhour.

Example 9

[0055] In this example,n⁵-cyclopentadienyl(N,N-bis(trimethylsilyl)amido)titanium(IV) dichloridewas used for this polymerization. 30 milliliters of 10 wt % MAO intoluene and 118 grams of 85 wt % DCPD in toluene were added to thereactor. 314 grams of an ethylene/dicyclopentadiene polymer mixture wereproduced. The polymer mixture was dried in a vacuum oven to produce adry weight of 6.1 grams yielding an activity of 610 grams ofethylene/dicyclopentadiene polymer per gram ofn⁵-cyclopentadienyl(N,N-bis(trimethylsilyl)amido)titanium(IV) dichlorideper hour.

Example 10

[0056] In this example, bis(n⁵-cyclopentadienyldichlorotitanium) oxidewas used for this polymerization. 120 milliliters of 10 wt % MAO intoluene and 472 grams of 85 wt % DCPD in toluene were added to thereactor. The ethylene/dicyclopentadiene polymer mixture was washed threetimes with acetone and then three times with methanol. It was then driedin a vacuum oven to produce 119 grams of dry polymer which yielded anactivity of 2975 grams of ethylene/dicyclopentadiene polymer per gram ofbis(n⁵-cyclopentadienyldichlorotitanium) oxide per hour.

Example 11

[0057] In this example,n⁵-cyclopentadienyl(3,5-di-tert-butylphenoxy)titanium(IV) dichloride wasused for this polymerization. 30 milliliters of 10 wt/o MAO in tolueneand 300 grams of 89.2 wt % DCPD in toluene were added to the reactor.The ethylene/dicyclopentadiene polymer mixture was washed twice withacetone. It was then dried in a vacuum oven to produce 38.90 grams ofdry polymer which yielded an activity of 5210 grams ofethylene/dicyclopentadiene polymer per gram ofn⁵-cyclopentadienyl(3,5-di-tert-butylphenoxy)titanium(IV) dichloride perhour.

Example 12

[0058] In this example,n⁵-cyclopentadienyl(3,5-di-tert-butylphenoxy)titanium(IV) dichloride wasused for this polymerization. 30 milliliters of 10 wt % MAO in tolueneand 300 grams of 86.8 wt % DCPD in toluene were added to the reactor.The ethylene/dicyclopentadiene polymer mixture was washed with acetone.It was then dried in a vacuum oven to produce 19.88 grams of dry polymerwhich yielded an activity of 4580 grams of ethylene/dicyclopentadienepolymer per gram ofn⁵-cyclopentadienyl(3,5-di-tert-butylphenoxy)titanium(IV) dichloride perhour.

Example 13

[0059] In this example, n⁵-cyclopentadienyl titanium (IV) trichloridewas used for this polymerization. 30 milliliters of 10 weight percentMAO in toluene, 100 grams of 97.96 weight percent DCPD in toluene and200 milliliters of toluene were added to the reactor. Theethylene/dicyclopentaidene polymer mixture produced was washed withacetone. It was then dried in a vacuum oven to produce 118.90 grams ofdry polymer which yielded an activity of 11890 grams ofethylene/dichclopentadiene polymer per gram of n⁵-cyclopentadienyltitanium (IV) trichloride per hour.

Example 14

[0060] In this example, n⁵-cyclopentadienyl titanium (IV) trichloridewas used for this polymerization. 30 milliliters of 10 weight percentMAO in toluene, 270 grams of 97.96 weight percent DCPD and 30 ml toluenewere added to the reactor. The ethylene/dicyclopentadiene polymermixture was washed three times with methanol. It was then dried in avacuum oven to produce 91.70 grams of dry polymer which yielded anactivity of 9170 grams of ethylene/dicyclopentadiene polymer per gram ofn⁵-cyclopentadienyl titanium (IV) trichloride per hour. TABLE I TitaniumComplex Wt. % of Titanium Amount MAO Ethylene DCPD Temp. Toluene PolymerDCPD Example Complex (g) (ml) (psig) (g) (° C.) (ml) (g) in PolymerActivity* 1 Catalyst 1 0.01 10 300 50 70 200 0.8 80 2 Catalyst 1 0.01 10300 110 70 200 2.9 290 3 Catalyst 1 0.01 30 300 110 70 200 35.6 12.63560 4 Catalyst 2 0.01 30 300 110 70 200 51.4 5140 5 Catalyst 3 0.01 30300 118 70 200 13.9 1390 6 Catalyst 3 0.01 30 300 118 70 200 46.7 4650 7Catalyst 2 0.01 30 300 118 70 200 41.4 26.2 4140 8 Catalyst 2 0.01 30300 118 70 200 24.9 13.6 2490 9 Catalyst 4 0.01 30 300 118 70 200 6.1610 10 Catalyst 2 0.04 120 300 472 70 1200 119 23.4 2975 11 Catalyst 30.01 30 100 300 70 0 38.9 52.1 5210 12 Catalyst 3 0.01 30 50 300 70 019.88 45.8 4580 13 Catalyst 5 0.01 30 300 100 70 200 118.90 — 11890 14Catalyst 5 0.01 30 300 270 70 30 91.7 — 9170

[0061] While this invention has been described in detail for the purposeof illustration, it is not intended to be limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

That which is claimed is:
 1. A process to produce adialkenyl-tricyclic-nonaromatic/olefin polymer said process comprisingcontacting at least one dialkenyl-tricyclic-nonaromatic compound, atleast one olefin, at least one titanium complex catalyst, and at leastone aluminoxane in a polymerization zone under polymerization conditionsto form said polymer; wherein said dialkenyl-tricyclic-nonaromaticcompound has the formula:

wherein R is selected from the group consisting of hydrogen and alkylgroups having from 1 to about 4 carbon atoms; wherein said titaniumcomplex has the following general formula: (X¹)(X²)(X³)(X⁴)M¹ wherein M¹is titanium; wherein (X¹) is independently selected from the groupconsisting of cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls;wherein substituents on the substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls of (X¹) are selected from the groupconsisting of aliphatic groups, cyclic groups, combinations of aliphaticand cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, oxygengroups, such as alkoxides and aryloxides, silicon, phosphorus, boron,germanium, and hydrogen; wherein (X²), (X³), and (X⁴) are independentlyselected from the group consisting of halides, aliphatic groups,substituted aliphatic groups, cyclic groups, substituted cyclic groups,combinations of aliphatic groups and cyclic groups, combinations ofsubstituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic groups and substituted cyclic groups, amidogroups, substituted amido groups, phosphido groups, substitutedphosphido groups, alkoxide groups, substituted alkoxide groups,aryloxide groups, substituted aryloxide groups, organometallic groups,and substituted organometallic groups.
 2. A process according to claim 1wherein said olefin contains 2 to about 10 carbon atoms.
 3. A processaccording to claim 2 wherein said dialkenyl-tricyclic-nonaromaticcompound is dicyclopentadiene.
 4. A process according to claim 3 whereinsaid olefin is ethylene.
 5. A process according to claim 4 wherein saidtitanium complex is selected from the group consisting ofn⁵-cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titanium(IV)dichloride, bis(n⁵-cyclopentadienyldichlorotitanium) oxide,n⁵-cyclopentadienyl(3,5-di-tert-butylphenoxy)titanium(IV) dichloride,and n⁵-cyclopentadienyl(N,N-bis(trimethylsilyl)amido)titanium(IV)dichloride, and n⁵-cyclopentadienyl titanium (IV) trichloride, andmixtures thereof.
 6. A process according to claim 5 wherein saidpolymerization zone is a solution process or a slurry process.
 7. Aprocess to produce an ethylene/dicyclopentadiene polymer comprisingcontacting: 1) n⁵-cyclopentadienyl titanium(IV) trichloride 2) ethylene;3) dicyclopentadiene; and 4) methylaluminoxane; in a solutionpolymerization process under polymerization conditions to produce saidethylene/dicyclopentadiene polymer.
 8. A polymer produced by claim
 1. 9.A polymer produced by claim
 7. 10. Adialkenyl-tricyclic-nonaromatic/olefin polymer consisting essentially ofat least one polymerized dialkenyl-tricyclic-nonaromatic compound and atleast one polymerized olefin.
 11. Adialkenyl-tricyclic-nonaromatic/olefin polymer according to claim 10wherein said at least one polymerized dialkenyl-tricyclic-nonaromaticcompound is dicyclopentadiene and wherein said at least one polymerizedolefin is ethylene.
 12. A normally solid ethylene/dicyclopentadienepolymer characterized by being soluble at 70° in toluene.
 13. An articleproduced from the polymer of claim
 10. 14. An article produced from thepolymer of claim 11.